Hydrogen Production from a Methanol–Water Solution Catalyzed by an Anionic Iridium Complex Bearing a Functional Bipyridonate Ligand under Weakly Basic Conditions

An efficient catalytic system for the production of hydrogen from a methanol–water solution has been developed using a new anionic iridium complex bearing a functional bipyridonate ligand as a catalyst. This system can be operated under mild conditions [weakly basic solution (0.046 mol L^?1 NaOH) below 100 °C] without the use of an additional organic solvent. Long‐term continuous hydrogen production from a methanol–water solution catalyzed by the anionic iridium complex was also achieved.     

Colorimetric detection of Cu2+ using of a mixture of ponceau 6R and a cationic polyelectrolyte in aqueous solution

Journal of Inclusion Phenomena and Macrocyclic Chemistry - A colorimetric chemosensor is reported for Cu2+ by a simple mixture of two commercially available reagents, ponceau 6R (P6R) and...     

Phase structure change and ER effect in liquid crystalline polymer/dimethylsiloxane blends

The mechanism of the electrorheological (ER) effect in two types of liquid crystalline polymer (LCP)/dimethylsiloxane (DMS) blends was investigated by rheological measurements and by structure observation under electric field and shear flow. The results show that the phase structures of these immiscible blends can be categorized into slipping (low viscosity) and non-slipping (high viscosity) states. In the non-slipping state, higher viscosity LCP domains connect the electrodes. In the slipping state, on the other hand, LCP domains do not connect the electrodes and the shear is mainly confined in the lower viscosity DMS domains. The ER effect (electrically induced viscosity increase) originates from the electrically induced slipping to non-slipping transition. In one of the blends, the ER effect occurs only at high shear rate, since this blend is in non-slipping state even under no field if the shear rate is low. Received: 29 April 1997 Accepted: 3 November 1997     

Formation of double helix self-assembled monolayers of ethynylhelicene oligomer disulfides on gold surfaces

Optically active ethynylhelicene pentamers and hexamers linked by disulfide bonds were synthesized. They formed self-assembled monolayers (SAMs) with double helix structure on gold surfaces, which were analyzed by infrared reflection-absorption spectroscopy (IR-RAS), quartz crystal microbalance (QCM), surface plasmon resonance (SPR), and circular dichroism (CD). Double helix SAMs could be formed on gold surfaces either from double helices or random coils in solution. The double helices on the surface were more stable than in solution. This result suggested the presence of strong intercomplex interactions between double helix complexes on the surface.     

Synthesis of Optically Active Aromatic Ether Ketone Macrocycles Containing 2,2′-Dimethoxy-1,1′-binaphthyl-6,6′-diyl Moieties

Optically active aromatic ether ketone macrocycles containing 2,2′-dimethoxy-1,1′-binaphthyl-6,6′-diyl moieties were synthesized through electrophilic aromatic substitution reaction and stepwise nucleophilic aromatic substitution reactions. Structures of the resulting macrocycles were confirmed by NMR and matrix assisted laser desorption/ionization time of flight (MALDI-TOF) mass measurements.     

Colorimetric detection of spermine and spermidine by zincon in aqueous solution

The anionic organic dye, zincon, was found to be a colorimetric probe for spermine and spermidine at pH 4.0 in pure aqueous solution through its aggregation by electrostatic interactions with them. The addition of spermine and spermidine led to bathochromic shifts with color changes from yellow to purple and dark brown, respectively, while other amines and basic amino acids induced no or minimal spectral and color changes. From Job’s plot and titration experiments, zincon interacted with spermine (+4 charges) and spermidine (+3 charges) in 4:1 and 3:1 stoichiometric ratios, respectively, indicating that each positive charge was bound to one zincon molecule. The detection limits were determined to be 25.1 for spermine and 30.7 nM for spermidine, which were sufficient below the critical concentration for cancer diagnosis. The results indicated that zincon can be a good candidate for simple, convenient colorimetric detection of spermine and spermidine in aqueous solution.     

Oxidative coupling polymerization of 2,3‐dihydroxynaphthalene with dinuclear‐type copper(II) catalyst

The oxidative coupling polymerization of 2,3‐dihydroxynaphthalene with the novel dinuclear‐type copper(II) catalysts successfully produced poly(2,3‐dihydroxy‐1,4‐naphthylene). For example, the MeOH‐insoluble polymer with a number average molecular weight of 4.4 × 10³ from the polymerization using the complex of CuCl₂ and N,N′‐bis(2‐morpholinoethyl)‐p‐xylylenediamine ( p ‐ 1 ) at room temperature under an O₂ atmosphere followed by acetylation of the hydroxyl groups was obtained in 63% yield. The structures of the tetraamine ligands and the counter anion of the copper(II) salts significantly influenced the catalyst activity. The polymerization of 2,2′‐dimethoxy‐1,1′‐binaphthalene‐3,3′‐diol with the 2CuCl₂‐ p ‐ 1 catalyst, however, resulted in a lower yield. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1635–1640, 2005     

Quantum coherence in quantum dot—Aharonov–Bohm ring hybrid systems

We investigate coherent transport through hybrid systems of quantum dots and Aharonov–Bohm (AB) rings. Strong coherence over the entire system leads to the Fano effect, which originates from the interference and the phase shift caused by the discrete states in the dots. The high controllability of the system parameters reveals that the Fano effect in mesoscopic transport can be a powerful tool for detecting the phase shift of electrons. We apply it to detect electrostatic phase modulation and the phase shift in a quantum wire with a side-coupled dot. Finally, we provide an experimental answer to the problem of “neighboring in-phase Coulomb peaks”.     

Coordination of aluminum in amorphous sodium aluminosilicate films

Amorphous sodium aluminosilicate thin films containing large amounts of Al₂O₃ were deposited on fused silica substrates by rf-sputtering, and their aluminum K-band X-ray emission spectra were measured by using an electron probe X-ray microanalyser in order to determine the coordination number of aluminum ions in the amorphous thin films.

The chemical shifts for the amorphous films with Al₂O₃/Na₂O<1 were almost identical with those of tetrahedrally coordinated aluminum ions in microline. On the other hand, for the amorphous films with Al₂O₃/Na₂O>1, the chemical shifts increased with increasing Al₂O₃/NA₂OF ratio, approaching that of amorphous alumina. From the comparison with the chemical shifts of -Al₂O₃ and mullite, the coordination state of aluminum ions in amorphous alumina was found to be about 5, and its structure was found similar to be that in crystalline Al₂O₃ with spinel-type structure. These results indicate that in amorphous sodium aluminosilicate thin films aluminum ions exist in the tetrahedrally coordinated state when the Al₂O₃/Na₂O ratio is nearly equal to or less than unity. However, when the Al₂O₃/Na₂O ratio exceeds unity, some of the aluminum ions begin to assume the octahedrally coordinated state and increase in number with increasing Al₂O₃/Na₂O ratio.     

Boundary Harnack Principle for <Emphasis Type="Italic">p</Emphasis>-harmonic Functions in Smooth Euclidean Domains

We establish a scale-invariant version of the boundary Harnack principle for p-harmonic functions in Euclidean C ^1,1-domains and obtain estimates for the decay rates of positive p-harmonic functions vanishing on a segment of the boundary in terms of the distance to the boundary. We use these estimates to study the behavior of conformal Martin kernel functions and positive p-superharmonic functions near the boundary of the domain. H. A. was partially supported by Grant-in-Aid for (B) (2) (No. 15340046) Japan Society for the Promotion of Science. N. S. was partially supported by NSF grant DMS-0355027. X. Z. was partially supported by the Taft foundation.